MX2007014763A - An integrated on-line two-dimensional method and device for synchronized analytical temperature rising elution fractionation and gel permeation chromatography. - Google Patents

Abstract

An analytical method comprising performing a first fractionation of a polymer sample based on differences in crystallizability to provide a first set of sample fractions, performing a first analysis on the first set of sample fractions, performing a second fractionation of the first set of sample fractions to produce a second set of sample fractions, performing a second analysis on the second set of sample fractions, and synchronizing the first fractionation and second fractionation to provide about concurrent analysis of the polymer sample.

Description

A TWO-DIMENSIONAL INTEGRATED LINE METHOD AND DEVICE FOR FRACTIONATION OF SYNCHRONIZED ANALYTIC TEMPERATURE ELEVATION ELUTION AND GEL PERMEATING CHROMATOGRAPHY FIELD OF THE INVENTION The present invention relates to polymer characterization and more particularly to the simultaneous analysis of chemical composition distribution and molecular weight distribution of a polymer sample using a combination of elution fractionation of analytical temperature elevation (aTREF) and chromatography. permeation on fast gel (rGPC).

BACKGROUND OF THE INVENTION Knowledge of polymeric microstructure is critical to understanding the potential utility of a polymer blend. The analysis of the polymeric microstructure is usually based on analytical techniques capable of providing data on the chemical composition, molecular weight and molecular weight distribution (MW / MWD) of a polymer sample. The temperature rise elution fractionation (TREF) separates the polymer molecules based on their crystallization capacity. The separation of the TREF is a two-stage process in which a dissolved polymer sample is deposited on a column filled with inert packed material by programmed cooling of the column. The sample was redissolved within the flow solvent or mobile phase by slowly raising the column temperature while rinsing the column with solvent. The temperature at which the polymer fractions elute outside the column is primarily a function of the degree of short chain branching (SCB) within the sample, the molecular weights, and the thermal history that the polymer has experienced. The TREF analysis can be carried out in two grades depending on the amount of the sample that is fractionated. Normally, a polymer sample is analyzed using a preparation rate or pTREF in order to generate enough sample after fractionation to carry out further characterization of the polymer microstructure. Analytical grade TREF or aTREF is considered an improvement over the pTREF because the technique requires less polymer sample and the quantity of the eluent polymer sample can be monitored using an in-line detector. However, an aTREF analysis only provides limited information on the polymer microstructure. One limitation of an aTREF analysis is that aTREF does not differentiate between polymers that have similar melting points / elution temperatures, even dramatically different molecular weights, molecular weight distributions, SCB distribution through the molecular weight distribution and distribution of long chain branching through the molecular weight distribution. In addition, the information obtained from pTREF is not necessarily applicable to aTREF because there are differences in thermal histories experienced by the polymer in the two processes. Gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC), is a useful technique to characterize the molecular weight or molecular weight distribution (MW / MWD) of a polymer sample. The separation is achieved by injecting the sample into a column packed with a porous packed material such as a crosslinked poly (styrene-co-divinylbenzene) gel. Without wishing to be limited by theory, the GPC separation is based on differences in hydrodynamic volume. Very large molecules that enter the small pores in the packaging material are eluted from the first column while those that can enter the small pores require a longer time or larger elution volume to elute from the column. The routine characterization of a polymeric microstructure requires information from both TREF and GPC analyzes. A major impediment to using both TREF and GPC for characterization of polymeric microstructure is the need to carry out the offline analysis of the polymer sample fractions isolated from TREF before subjecting the polymer sample fractions to GPC analysis. This off-line processing of the polymer sample first by fractionation of pTREF, collecting the fractionated samples and then by GPC is very tedious. To complete a complete pTREF run with off-line GPC analysis for a polymer sample, usually two to three months are required, depending on the number of individual thermal interruptions analyzed. There is therefore a need for a fast and reliable two-dimensional technique that simultaneously determines the chemical composition and MW / MWD for a given temperature fraction.

SUMMARY OF THE INVENTION An analytical method comprising fractionating a polymer sample based on differences in crystallization capacity to obtain sample fractions is described herein; and characterizing the polymer sample by determining at the same time a composition and a molecular weight distribution of the fractions of the sample. Fractionation can be done through a temperature gradient. The molecular weight distribution can be determined by size exclusion chromatography. Size exclusion chromatography can be rapid gel permeation chromatography. The method may further comprise heating the sample fractions before rapid gel permeation chromatography. The method may further comprise implementing a valve scheme to complete the simultaneous determination of the composition and molecular weight distribution. The method may further comprise a computerized control for the simultaneous determination of the composition and molecular weight distribution. The simultaneous determination of the composition and molecular weight distribution can comprise the operation of an integrated device having the synchronized capabilities of an analytical temperature rise elution fractionation (aTREF) and fast gel permeation chromatography (rGPC). The simultaneous determination of the composition and the molecular weight distribution can be an online and / or real-time process that can be represented graphically. The graphic representation can simultaneously present data on the polymer composition, the molecular weight and the molecular weight distribution.

Also described herein is a device for characterizing a polymer sample comprising a first column for fractionating a polymer sample by a temperature gradient (TGC); a polymer composition detecting device in fluid communication with the first column to receive a first portion of the fractions of the polymer sample; at least one second column in fluid communication with the first column to receive a second portion of the fractions of the polymer sample, wherein the second column further separates polymers from the fraction; a second detection device in fluid communication with the second column to receive the polymers separated from the fraction and characterize a physical property thereof; and a computer that synchronizes the operation of the TGC and at least a second column for simultaneous determination of the chemical and physical properties of the polymer sample. The device may further comprise a valve scheme that regulates the transmission of polymer samples within the first column. The second column can separate polymers from the fraction based on molecular size and / or chemical composition. The device may comprise the capabilities of an integrated and synchronized aTREF apparatus and a rGPC, and in particular where the first column is part of the aTREF apparatus (e.g., a temperature gradient column) and the second column is part of the rGPC apparatus (eg, a molecular weight column). The valve scheme may comprise multiport valves. There is further described an analytical method comprising introducing a sample to an analytical device having synchronized aTREF and rGPC elements; operate the analytical device; and determining the concentration, molecular weight and molecular weight distribution of a polymer sample of a polymer sample in less than about 8 hours. Further described is an analytical method comprising fractionating a polymer sample based on differences in crystallization capacity to obtain sample fractions; detect any composition of the sample fractions; separating any polymers in the sample fractions based on differences in molecular weight; detecting any molecular weight distribution of polymers in the sample fractions; and characterizing the polymer sample, wherein the composition and molecular weight distribution are determined simultaneously.

BRIEF DESCRIPTION OF THE FIGURES The invention, together with additional advantages thereof can be better understood by reference to the following description taken together with the accompanying figures in which: Figure 1 is a schematic representation of an aTREF-rGPC device. Figure 2 is a flowchart representing a modality of the components of an aTREF-rGPC device. Figure 3 is a flow diagram of a multi-port injection valve in the I position. Figure 4 is a flow chart of a multi-port injection valve in the II position. Figures 5A and 5B depict an exploded view of a multi-port injection valve. Figure 6 is a color graphic representation of data obtained from an aTREF-rGPC device. Figure 7 is a two-dimensional color graphical representation of a polymer sample characterized by the aTREF-rGPC device. Figure 8 represents a profile profile of graphical contour of data obtained from the characterization of a polymer sample by an aTREF-rGPC. Figure 9 is a two-dimensional color graphical representation of data obtained from the characterization of a polymer sample by an aTREF-rGPC. Figure 10 is a three-dimensional presentation of the aTREF-rGPC data for sample A in Example 2. Figure 11 is a graph of the total molecular weight distribution profile for Sample A in Example 2. Figure 12 is a graph of the total aTREF profile for Sample A in Example 2. Figure 13 is a two-dimensional contour plot for Sample A in Example 2. Figure 14 is a graph of fractional molecular weight distribution profiles of aTREF of Sample A in Example 2. Figure 15 is a graph of fractions of aTREF at a given molecular weight for Sample A in Example 2. Figure 16 is a two-dimensional contour plot for Sample B in Sample Example 3. Figure 17 is a two-dimensional contour plot for Sample C in Example 4. Figure 18 is a two-dimensional contour plot for Sample D in Example 5. Figure 19 is a two-dimensional contour plot for Mu E in Example 6.

Figure 20 is a two-dimensional contour plot in a limited temperature range for Sample E in Example 6.

DETAILED DESCRIPTION OF THE INVENTION With reference to Figure 1, a device 100 comprises a system having the capabilities of aTREF ("aTREF system") coupled with a system having the capabilities of rGPC ("rGPC system") 400 As will be understood by a person skilled in the art, the term rapid GPC (rGPC) refers together to rGPC, accelerated GPC (fGPC), high performance GPC (htGPC), fast SEC (rSEC), accelerated SEC (fSEC), and high throughput SEC (htSEC) and further refers to GPC or SEC carried out in a shorter period of time than that associated with conventional GPC or SEC methods. The term rGPC is used throughout this description, and it will be understood that the term is representative of all GPC and / or SEC methods that can be conducted over a period of time compatible with the devices and methodologies described. The device ("aTREF-rGPC device") 100 is controlled, including the synchronization of the aTREF system 300 and the rGPC system 400, by a device controller 150. Systems 300, 400 and controller 150 can achieve synchronized online analysis of chemical samples, and in particular polymer samples. Online refers to electronic coupling (eg, network connection), operation, and communication of systems 300, 400 by controller 150, which can be implemented by one or more computers, microprocessors, controllers and the like. In one embodiment, the sample is any polymeric material whose solubility changes as a function of the temperature of the solvent. In an embodiment of Figure 1, the aTREF system 300 is coupled to the rGPC system 400, and the device controller 150 can control the two systems so that the data output from the two systems is synchronized in real time. In the embodiments, the aTREF system 300 and the rGPC system 400 can be coupled for simultaneous online operation. In some embodiments, an aTREF system 300 and a rGPC system 400 are part of a linked, integrated device combined within a common housing or assembly. For example, the aTREF unit and the rGPC unit can be connected through a heat transfer line whose temperature is adjusted to match that of the rGPC column / detector compartment. In various embodiments, an aTREF-rGPC device is a device for characterizing a polymer sample. Such a device may comprise: a column packed with inert hard spheres that fractionate polymers by a temperature gradient for example by elution fractionation of temperature rise ("TREF column" or "TC"); a polymer composition detecting device; a column for separating polymers according to their size (or hydrodynamic volume) ("molecular weight column" or "MWC"); a polymer concentration detection device; a valve scheme that regulates the transmission of the sample fractions to the MWC; and a computer performing the synchronized operation of the CT and MWC for simultaneous determination of the composition, molecular weight and molecular weight distribution of the polymer sample. Here, the detection of the polymer composition may include the detection of the primary structure, the secondary structure, the polymeric tertiary structure or combinations thereof. As will be understood by one skilled in the art, the polymeric primary structure refers to how a simple polymer chain is grouped. For example, the primary structure can refer to the chemical composition of the polymer and the types of branching in the polymer. The secondary structure refers to the three-dimensional conformation of the polymer and the polymer chain configuration. Examples of secondary structure include conformations such as random coil, folded chain and spiral chain or helix. The polymer chain configuration can not be changed without breaking or changing the shape of the primary (covalent) bonds. The tertiary and higher structure refers to the interactions of a polymer chain with another polymer chain. Examples of tertiary structure include, for example, overspray, also known as super spiral. The polymeric morphology is included in the tertiary structures. In one modality, fractionation through a CT is achieved through TREF. A device for characterizing a polymer sample may comprise the capabilities of an aTREF system in order to determine the polymer composition in the sample. In one embodiment, a column for separating polymers can be separated through size exclusion chromatography, such as by rGPC. In addition, a device for characterizing a polymer sample may comprise the capabilities of a rGPC system in order to determine the molecular weight distribution within a polymer fraction. In some embodiments, a fractionation based on different methods of the combination of an aTREF and rGPC can be carried out. For example, aTREF can be coupled to a device that separates a polymeric material based on the chemical composition such as a hydrophobic interaction column, an ion exchange column, a high resolution liquid chromatography (HPLC) column or combinations of the same. In one embodiment, the aTREF column can be coupled to any column capable of fractionating a polymeric material that is eluted from an aTREF column. Such devices would be subject to the design and controls described herein. In the modalities, an aTREF-rGPC device integrates and synchronizes the capabilities of an aTREF system and a rGPC system. In some embodiments, such a device comprises a valve scheme, such as a valve scheme including a six port valve (SPIV), which regulates the transmission of polymer fractions to a MWC. A device and method for characterizing a polymer sample can be illustrated for reference to the embodiment of Figure 2. The aTREF-rGPC device 100 of Figure 2 comprises the elements described in Figure 1; the controller 150, a system 300 of aTREF, and the system 400 of rGPC. In addition, Figure 2 illustrates some embodiments of the components and functionality in each of the systems 300 and 400. A polymer solution can be introduced to the aTREF-rGPC device 100 through the line 190 in the sample injection device 10. . The sample injection device 10 can be housed in a heating furnace 35, which can also house the temperature equilibrium coil 15 and an aTREF column 25. Line 190 may represent any method used by one skilled in the art to deliver a polymer sample to an aTREF system. The controller 150 as indicated by the connection 904 can operate the heating oven 35, and the components housed inside the heating oven 35. The temperature of the heating furnace 35, and the column 25, the sample injection device 10, and the temperature equilibrium coil 15 housed within the heating furnace 35, can be operated or manually coupled to, and operated by the controller 150. of device via connection 904. In one embodiment, the heating furnace 35 and the components it houses can be cooled and heated in a temperature range from about 25 ° C to about 250 ° C at an index of 0.1 ° C to 20 ° C / minutes. In the present embodiment, a suitable solvent originating from the solvent reservoir 5 can carry the polymer sample from the sample injection device 10 through line 198 to column 25 of aTREF. In an alternative embodiment, an appropriately solubilized polymer sample may be introduced directly into the column of aTREF. A suitable solvent is one employed by those skilled in the art, which remain generally inert and liquid under the process conditions described. Examples of suitable solvents for polyolefins include but are not limited to 1, 2, 4-trichlorobenzene, o-dichlorobenzene, 1,3,5-trimethylbenzene, 1-chloronaphthalene and xylene. In one embodiment, the solvent is any material capable of dissolving the polymer sample (eg, a semicrystalline polymer) and which is chemically compatible with the sample and the aTREF-rGPC device. The solvent originating from the solvent reservoir 5 can be transported via line 195 and line 200 by the pump 30. The solvent pre-heater 40 can heat the solvent as it passes along line 200 to the furnace 35 of heating. The solvent preheater 40 and the temperature equilibrium coil 15 can appropriately set the solvent feed temperature to the sample injection device 10 and a column of aTREF. In the valve 144, the solvent can be routed to the heating furnace 35 where it reaches the aTREF column 25 by a flow path comprising the line 201, the temperature equilibrium coil 15, line 194, the injection device 10 sample and line 198.

Alternatively, at valve 144 the solvent can be routed to line aTREF column 25 through line 202. Pump 30, solvent pre-heater 40, and valve 144 can each be manually operated or operated by the controller 150 through connections 901, 902 and 903, respectively. The check valve 20 regulates the flow of solvent from line 202 to line 203, and in particular can prevent backflow resulting from transports from line 199 to lines 203. Check valve 20 can be a static device (ie "passive") that does not require operation or can be operated manually or can be regulated by controller 150, as indicated by connection 905. Figure 3 provides a more detailed illustration of a mode of a heating furnace 35, which is shown in Figure 2 as a part of the aTREF system 300 in the aTREF-rGPC device 100. As in Figures 2 and 3, the heating furnace 35 comprises an aTREF column 25, a temperature balancing coil 15, and a sample injection device 10. In the embodiment of Figure 3, the sample injection device 10 comprises a multi-port valve 71, a sample tube 73 and a syringe 74. In one embodiment shown in the Figures, the multi-port valve 71 is a six-way valve. ports having ports 1-6A, which is referred to herein as SPIV 71. It should be understood that other multiport configurations may be used having an adequate number of ports for a desired operational configuration. For example, duplicate or multiple components (which may be the same or different) within the sample device 10 such as solvents, sample tubes, syringes, polymer sample containers, and outputs to aTREF column 25, may be placed in fluid communication through one or more appropriately configured multiport valves. In one embodiment, one or more multiport valves are in fluid communication with one or more additional multiport valves. The embodiment of Figure 3 further comprises a polymer sample container 72, which provides polymer samples to the polymer sample injector 10 through line 190. The solvent is fed through line 201 to the coil 15. of temperature equilibrium, which further passes the solvent to the sample injection device 10 through line 194. Transportation from sample injection device 10 to column 25 of aTREF is through line 198, and the transport on the downstream side (for example, above) of the column 25 is through the line 199. The line 190 of Figure 2 corresponds to the line 190 leaving the polymer sample container 72 of the Figure 3, which carries polymer samples to the sample injection device 10. The direction arrows 600 of 604 and 611 to 616 indicate the flow directions in the lines of Figure 3 when SPIV 71 is in a first loading position ("position I"). The SPIV configuration 71 illustrated in the embodiment of Figure 3 loads a polymer sample into the polymer sample injector 10. When SPIV 71 is in positions I, ports IA, 3A and 5A are connected to ports 2A, 4A and 6A, respectively. The solvent flow from the pump 30 is transported downstream, indicated by the direction arrow 600, through the line 201 to the temperature equilibrium coil 15. The solvent exiting coil 15 through line 194, indicated by direction arrow 601, then flows through SPIV 71 at ports IA and 2A, indicated by direction arrow 602, before leaving. SPIV 71 and flowing downstream through line 198, indicated by direction arrow 603, to column 25 of aTREF. In the embodiment of Figure 3, the polymer sample originates in the polymer sample container 72, so that it can be extracted to fill the sample tube 73 using the syringe 74. Extraction in the syringe 74 moves the polymer solution from the polymer sample container 72 to the port 5A of SPIV 71 through the line 190, as it is indicated by the arrow 611 of direction. Port 5A is connected to port 6A as indicated by direction arrow 612 and the polymer sample can thus be transported through line 222 from SPIV 71 to sample tube 73, as indicated by direction arrow 613 . Extraction in the barrel of the syringe 74 can further move the polymer sample through the sample tube 73 and through the line 223 to the SPIV port 3A as indicated by the direction arrow 614. The sample of polymer (or other liquid, eg, pure solvent, in front of it) flows from port 3A to port 4A as indicated by direction arrow 615. Another hollow tube called a "removable crucible" 79 can be inserted between port 4A and syringe 74. Removable crucible 79 can operate to prevent the polymer solution from being drawn from barrel 74 of the syringe where the sample could be precipitated at a temperature environment and causing the line to jam and / or damage the syringe 74. In one embodiment, the removable crucible 79 is a hollow stainless steel crucible whose volume when added to the volume of the sample tube 73 is not less than the volume of the sample. the syringe 74. In an alternative embodiment, a polymer sample is inserted directly into the sample tube 73. In yet another embodiment, a pre-filled sample tube is placed in the solvent flow path to a column aTREF. An example of a sample tube 73 is a hollow stainless steel tube with fritted caps on both sides connected in line having a capacity of about 1 milliliter to about 100 milliliters. In this way, the set of SPIV in the position I allows the loading of a polymer sample in the sample tube 73. Meanwhile, the solvent can flow as needed by an operation of the pump 30 directly to column 25 of aTREF through line 200, lines 201, line 194, port IA, port 2A, and line 198, and consequently it skirts any polymer in the flow circuit comprising the sample tube 73. Figure 4 illustrates aTREF-rGPC device elements identical to those shown in Figure 3, but with modified flow paths. While the embodiment of Figure 3, ie, position I, allows loading of a polymer sample in the sample tube 73, the configuration illustrated by the embodiment of Figure 4 ("position II") injects the sample of polymer from sample tube 73 loaded into column 25 of aTREF. Thus, with SPIV 71 in the I position, a polymer sample can be loaded into the sample tube 73, and after the loading of SPIV 71 it can be switched to position II to complete the injection of the sample into the column 25. of aTREF. SPIV 71 can be controlled or manually coupled to and controlled by the device controller 150. In the embodiment of Figure 4, the II position of SPIV 71 has ports IA, 3A and 4A connected to ports 6A, 2A and 5A, respectively. The solvent flows from the temperature equilibrium coil 15 through line 194 into port IA as indicated by the direction arrow 601. SPIV 71 then directs the solvent to port 6A as indicated by direction arrow 622, and on sample tube 73 through line 222 as indicated by arrow 623. The polymer sample in tube 73 of Sample is transported downstream by the solvent, see direction arrow 624, from sample tube 73 through line 223 inside SPIV 71 at port 3A. The solvent also transports the polymer sample through SPIV 71 to port 2A as indicated by the direction arrow 625, and then through line 198 to column 25 of aTREF according to a direction arrow 626. Additionally, in position II, the syringe 74 can be used to push the polymer sample back into the sample container 72, thereby clearing the detachable crucible 79, line 224, port 4A, port 5A and line 190 as indicated by the arrows 631, 632 and 633. Alternatively, the syringe 74 may rinse or clean the lines with another liquid (e.g., fresh solvent), for example, using a substitute syringe loaded with a washing or pre-loading liquid with a liquid of washing before extracting the polymer sample from sample container 72 in position I. The transition of SPIV 71 between position I and position II, and the resulting charge and injection of the polymer sample, can be manually controlled , or be coupled to and controlled by the device controller 150. In embodiments, a column for fractionating a polymer sample by the temperature gradient ("TGC") as provided herein, such as an aTREF column, may be approximately 101-762 mm (4-30 inches) in length with an internal diameter of approximately 12 - 77 m (0.5 - 3.0 inches). Such a column can be packaged with a thermoset packing material having a loading capacity in the range of about 1 to about 100 ml. An example of a suitable packaging material includes, but is not limited to glass beads or 80 mesh sand. Referring again to the embodiment of Figure 2, the polymer sample loaded in column 25 of aTREF may then be cooled to allow crystallization of the polymer sample on the packing material in the column. A programmed temperature gradient allows the elution of the polymer sample fractions (PSFs) based on the crystallization capacity in the mobile phase of aTREF. The PSFs that elute from an aTREF column 25 on line 199 are transported through line 203 to the heating device 45. The heating device 45 can be a heating coil that is immersed in an oil bath, alternatively, the heating coil can be controlled by a programmable heating device. The heating device 45 can be used to maintain the PSF in the mobile phase of aTREF at a temperature suitable for rGPC. In an alternative embodiment, the heating device 45 can be manually controlled or controlled by the device controller 150 as indicated by the connection 907. In one embodiment, the line 203 can be coated or constructed of a material capable of good thermal conduction such as copper. A temperature regulator can then regulate the temperature of line 203 either manually or through the use of device controller 150. In one embodiment, the PSFs flow downstream from the heating coil 45 into a valve 50 that can split a PSF and direct a portion on the line 208 that feeds a detection system 55, while a second portion of the PSF is directed. on line 204 that transports the PSF to a 400 system of rGPC. Alternatively, the valve 50 may allow the flow of the complete PSF downstream through the line 208 to the detection system 55. And alternatively, the valve 50 may allow the flow of the complete PSF downstream through the line 204 to the rGPC system 400. In some embodiments, the detection system 55 is an element of an aTREF system 300. In one embodiment, the valve 50 can be controlled or manually coupled to and controlled by the device controller 150 through the connection 908. In one embodiment, the PSFs entering the line 208 can be analyzed by a detection system 55 to exit through line 209 and to be placed in a 58 waste depot. In the modality, the chemical composition of PSFs is analyzed by a spectrometer. Such a spectrometer can be measured in the infrared (IR) range. In some embodiments, the chemical compositions of PSFs are analyzed by a photometer. Such a photometer can be a low angle light diffusion photometer or a multiple angle light diffusion photometer. In some embodiments, the chemical compositions of PSFs are analyzed by viscosity measurements. The chemical composition of PSFs can be analyzed by any combination of spectrometer, photometer and viscosity detector. The detection system 55 can be a Fourier transform infrared detector (FTIR) 60, a multiple angle light diffusion detector (MALS) 65, a viscometer (VISC) 70, or any combination thereof. An example of a suitable infrared detector 60 is the Spectrum 2000 FT-IR commercially available from PerkinElmer. An example of a suitable viscometer 70 is the Viscotek viscometer: 150R commercially available from Viscotek. An example of a suitable multiple angle light scattering detector 65 is the Wyatt Dawn EOS Multiple Angle Light Diffusion detector commercially available from Wyatt Technology Corporation. The appropriate FTIR, MALS and VISC are those that could be employed by one skilled in the art. In one embodiment, the detection system 55 can be controlled or manually coupled to and controlled by the device controller 150, as shown by the connection 906. The rGPC system 400 of the aTREF-rGPC device 100 shown in the embodiment of the Figure 2 comprises a SPIV 75, MWC 110 (also known as a rGPC column) and a polymer concentration detection device 115. Similar to SPIV 71 in the sample injector 10 of the aTREF system 300 as shown in Figure 3 and Figure 4, SPIV 75 of the rGPC system 400 regulates injections of the PSFs in the MWC 110. Also, in the rGPC system 400 of Figure 2, line 206 supplies the solvent to SPIV 75. The solvent (eg, rGPC solvent) is contained in a solvent reservoir 85 and can be pre-treated and / or heated. For example, the solvent may pass through a degasser 90 before being transferred by the pump 95 through a filter 101 in line and on the SPIV 75. The solvent reservoir 85 may be the same as or different from the reservoir 5 of solvent, and in one modality, a common deposit is used. Figure 5 is an exploded view of the SPIV 75 which is a component of the rGPC system 400 of Figure 2. In the embodiment of Figure 5A, the position III directs the flow of the PSFs from the aTREF system 300, on line 204 through SPIV 75. Ports 5B and IB are connected to ports 4B and 6B, respectively. Online PSFs 204 enter SPIV 75 at port 5B and flow as indicated by direction arrow 651 through port 4B. Also, from port 4B, the PSFs flow as indicated by the directional arrows 652, 653, 654 and 655 through ports IB and 6B to line 220 and over the waste deposit 58. In this way, SPIV 75 can be set in position III in order to load the PSFs in SPIV 75 (more specifically charged in injector circuit 970) for further injection in MWC 110, as shown in Figure 2. While SPIV 75 is in position III, the solvent pumped from solvent reservoir 85 by pump 95 can skirt PSFs when flowing on line 206a SPIV 75 at ports 3B and 2B, as indicated by arrow 661 of direction and on the MWC 110 through the line 205. The selective operation of the pump 95 allows the pumping of the solvent to MWC 110 as is necessary, for example, to rinse the column. After loading the PSFs in the injector circuit 970 in the III position, the SPIV 75 can alternate to the IV position as indicated in Figure 5B. In position IV, ports 3B and IB of SPIV 75 are connected to ports 4B and 2B, respectively. The solvent from pump 95 on line 206 enters port 3B and flows to port 4B and to injector circuit 970 as indicated by direction arrows 681 and 682. In the IV position, the solvent transports the PSFs (charged while SPIV 75 is in position III) from the injector circuit 970 through ports IB and 2B, as indicated by arrows 683 and 684 of address. The solvent can also carry the PSFs from port 2B through line 205 to MWC 110. Meanwhile, the additional flow of PSFs from column 25 of aTREF is directed from line 204 at port 5B and over the port 6B as indicated by the direction arrow 671. Flow from an aTREF column 25 when SPIV 75 is in position IV sends the flow of the PSFs to residue 58 from port 6B through line 220. In this way, the flow of PSFs from an aTREF system 300 to a MWC 110 can be controlled by charging the PSFs for MWC 110 while SPIV 75 is in position III, and injecting the PSFs to MWC 110 when SPIV 75 is in position IV. The transition of SPIV 75 between positions III and IV can be manually controlled or coupled to and controlled by the device controller 150 through connection 909. In one embodiment, column 110 of MWC is less than about 20 cm in length and smaller than about 10 mm in diameter and allows the samples to be fractionated in less than about 10 minutes thus the term rapid GPC. Examples of suitable columns include, but are not limited to the PLgel column of 10 μM HTS-B which is commercially available from Polymers Labs (Amherst, MA) and the HSPgel HT MB-H column which is commercially available from Waters (Milford, MA). Examples of suitable GPC devices that can be adapted to perform fast GPC by an expert appropriately in the art include the Agilent 1100 Series SEC-GPC, commercially available from Agilent Inc., or the 150C SEC-GPC, commercially available from Waters and the PL220 GPC-SEC, commercially available from Polymer Labs. In the embodiment of Figure 2, the PSFs that elute from the MWC column 110 are transported by line 213 in the detection system 115. The detection system 115 can be controlled or manually coupled to and controlled by the device controller 150 as indicated by connection 910. The detection system can determine the molecular weight of the PSFs from the MWC column by an optical device. In one embodiment, such an optical device is measured in the infrared range. In another embodiment, such an optical device measures the differential refractive index. The PSFs in the MWC column can also undergo chemical composition analysis. Such chemical composition analyzes can be carried out through FTIR, a multiple angle light scattering detector, a viscosity detector, or combinations thereof. The PSFs that elute from the detection system 115 are transported through the lines 207 to the waste collection container 58.

In one embodiment, the detection system 115 may comprise a differential refractometer (DRI), a Fourier transform infrared detector (FTIR), a multiple angle light diffusion detector (MALS), a viscometer (VISC) or any combination thereof. The suitable DRI, FTIR, VISC and MALS are those which could be used by one skilled in the art. These detectors may be in addition to or in place of the detection system. For example, a detector arrangement equivalent to the detection system 55 could be placed on line 205 upstream of the MWC 110 or in parallel with the MWC 110 through a slipstream from the line 205. Such an arrangement can greatly simplify the synchronization of data for the object of MFPs to rGPC analysis, since only the samples loaded and injected through SPIV 75 could be subjected to the analysis through the detection system 115 and an equivalent detection system. The aTREF-rGPC device of Figure 2 employs a controller 150 in order to synchronize an aTREF system 300 and a rGPC system 400 for characterization of a polymer sample. In one embodiment, the analysis of the PSFs by detection systems 55 and 115 are synchronized, whereby compositional data and molecular weight distribution data are provided for each given PSF. In one embodiment, the synchronization occurs in real time, and can be implemented through the control system 150. For example, the control system 150 can capture data from the detection systems 55 and 115 at known intervals and matching data for those intervals, for example by clock synchronization, a counter or other incrementing device, or other synchronization means. In various embodiments, such synchronization may comprise: fractionating a polymer sample by a temperature gradient; detect the composition of the sample fractions; separating the polymers in the sample fractions based on differences in molecular weight; detecting the molecular weight and molecular weight distribution of polymers in the sample fractions; and characterizing the polymer sample based on the simultaneous determination of the composition, molecular weight and molecular weight distribution. The fractionation by the temperature gradient can also be referred to as fractionation based on the polymer crystallization capacity or fractionation through the polymer dissolution temperature. In embodiments, synchronization is achieved by employing controller 150 to coordinate a valve scheme comprising an SPIV 71 for injection of the samples into the aTREF system 300, and another SPIV 75 for injection of the samples into the rGPC system 400 . The controller 150 can regulate the positions of the valve 50 and the SPIV 75 in order to receive at the same time the molecular weight distribution and composition data for the same PSF from the detection systems 55 and 115. Meanwhile, the controller 150 can synchronize the determination of data through the detection systems 55 and 115 with injections of new polymer samples in the aTREF system 300 by the sample injection device 10 in order to achieve a process Online fully integrated. For example, a plurality of polymer samples may be made available through a corresponding plurality of the polymer sample container 72 and means for automatically changing the sample containers and for operating the syringe 74. In one embodiment, the controller 150 of The device can send a programmed signal to the rGPC system 400 to initiate the internal count when a sample is introduced to column 25 of aTREF, allowing the synchronization of the aTREF and rGPC subdivisions. Alternatively, the aTREF system 300 and the rGPC system 400 can be synchronized by the device controller 150, so that the device controller 150 signals the MWC column 110 to accept the sample injections from the SPIV 75 at fixed time intervals which normally correspond to the cycle time of the MWC 110. Alternatively, the aTREF system 300 and the rGPC system 400 can be synchronized by the device controller 150 by pointing to the MWC column 110 to accept the sample injections from the SPIV 75 at user defined ranges or profiles, for example, at predefined aTREF elution temperatures. In one embodiment, the device driver 150 may be a computer that activates software capable of synchronizing the acquired data of both rGPC and aTREF subdivisions. In one embodiment, a suitable computer is a digital computer, such as an IBM personal computer based on Pentium Intel, capable of receiving data entry from multiple detectors through serial interfaces. The computer may also be able to receive user input through a standard keyboard or other computer. In a modality described in Figure 6, the user interface of the system controller device 160 can display the rGPC and aTREF analysis results as individual graphs together with a contour plot of the synchronized analysis providing for example at a given elution temperature a corresponding molecular weight distribution profile and, at any given molecular weight, a corresponding aTREF profile. The resulting analytical data can be displayed in a plurality of windows which can be claied and arranged in a variety of configurations in the user interface (eg, display screen). With reference to Figure 6, displayed in the upper window is a total aTREF profile for the complete polymer sample. In an alternative embodiment, the top window can describe the aTREF profile for a portion of the polymer sample, for example, a portion having a particular molecular weight. Referring again to Figure 6, displayed in the lower left window is the total molecular weight distribution profile for the total polymer sample. In an alternative embodiment, the lower left window can describe the molecular weight distribution profile for a fraction of aTREF at a given elution temperature. The contour level in the lower right window of Figure 6 describes the product of the normalized weight fraction of a fraction of aTREF, records the times of differential intensity (ie, dw / d (Log M)) in a profile of molecular weight distribution at a given molecular weight. In one embodiment, the synchronization of the aTREF-rGPC device from the aTREF fractionation results and the rGPC separation provides a continuous two-dimensional online process wherein each fraction of rGPc represents the composition of the aTREF eluent for a temperature range of less than about 0.05 ° C. In some embodiments, a full two-dimensional analysis of a polymer sample by the description can be carried out by the aTREF-rGPC device in less than about 24 hours, alternatively, less than about 20 hours, alternatively less than about 16 hours, alternatively less than about 12 hours, or alternatively less than about 8 hours.

EXAMPLES Having described the invention in general, the following examples are given as particular embodiments of the invention and to demonstrate the practice and advantages thereof. It is understood that the examples are given by way of illustration and are not intended to limit the specification of the claims that follow in any way.

EXAMPLE 1 A computer simulation of an aTREF-rGPC apparatus and method described above was prepared and used to simulate the fractionation of a polymer sample containing a short chain branched polyethylene resin such as a low density polyethylene resin (LDPE). ) or linear low density polyethylene (LLDPE) resins from Chevron Phillips Chemical Company LP. The data acquisition and data processing software of rGPC were PE Nelson (Model 2600 Multiple Instrument Chromatography Software 1988-1992, Perkin Elmer Corp.) and Chevron Phillips Chemical in-house DRPolymer Software. However, commercially available software may be used. An example of software suitable for processing and data acquisition is the Cirrus Multidetector Software commercially available from Polymer Laboratories. The graphic software used for the 3D graphics was SigmaPlot for Windows Version 4.0 of SPSS Inc. The LLPDE samples are composed of branched molecules with several levels of single chain branching. During the simulation of LLPDE resin it is dissolved in 1,2,4-trichlorobenzene. As illustrated by Figure 2, solubilized LLPDE was injected into the sample injection device 10 at a solvent flow rate of 0.5 ml / minute. The LLPDE sample was loaded onto an aTREF column that was 152 mm (6 inches) long with an internal diameter of 12 mm (0.5 inches) and was packed with # 30 SS Shot obtained from Vulcan Blast Technology. The computer was programmed to raise the temperature at an index of 0.5-1.5 ° C / minute with a temperature rise interval of 35 ° C to 125 ° C and a total rise time of between 60 to 180 minutes. The LLPDE fractions eluting from the aTREF column were injected onto the rGPC column through SPIV 75 at temperatures of 35, 40, 45, 50, 55, 65, 75, 85, 95, 105 and 110 ° C . The rGPC column was a commercially available PL Rapide column from Polymer Labs that was 10 cm in length and 10 mm in diameter. SPIV 75 had a 970 injector circuit size in the range of 100 μl to 500 μl. The LLPDE samples loaded on the rGPC column were activated at a flow rate of 0.5 -1.0 ml / minute at a temperature of 140 ° C. The rGPC data acquisition software recorded the polymer concentration as a function of elution time. The aTREF data acquisition software recorded chemical composition data as a function of elution temperature. Since the system's flow rate of rGPC is a constant, a new chromatogram is a plot of concentration c as a function of the volume of elution Ve. In order to convert the new chromatogram into the MWD profile, a calibration is performed using a set of narrow MWD polymers whose MW is already known under the same activation conditions used to fractionate the LLPDE sample. A calibration curve, log M against elution volume Ve for the standard can then be established. Coupling the new chromatogram (c - Ve) with the calibration curve, Log M - Ve, elution volumes in the new chromatogram can become Log M. By using the following equation, the average MW number (Mn), the average in weight and the polydispersity index (Mw / Mn) can be calculated. M2 = S (C./M / S (c) Digitalized rGPC data were saved as the concentration time-elution (volume) data pairs in computer storage devices with various data structures Figure 7 is a graph two-dimensional of fractionation of the LLDPE resin using the simulation of an aTREF-rGPC apparatus diagrammed in Figure 2. The two-dimensional data set shown in Figure 7 was constructed by plotting the elution temperature (temperature) v. molecular weight v. Heavy weight fraction (dw / d (log M)). The simulated aTREF-rGPC apparatus fractionated the LPDE sample into three peaks. Peak 1 is the narrow peak at approximately 40 ° C in Figure 7 and corresponds to the soluble fraction of room temperature of the LLPDE sample. The soluble fraction of room temperature of the LLPDE sample contains highly branched polymers that do not crystallize even at room temperature. Peak 2 is the broad peak in the average temperature range occurring at approximately 75 ° C and corresponds to a fraction of the LLPDE sample consisting of branched molecules with a branching content of several single chains. Peak 3 is a defined peak observed at approximately 105 ° C and corresponds to a fraction of the LLPDE sample consisting of high density polyethylene and polyethylene homopolymers. Project the data in 3D to the x-plane and resulted in the contour plot of molecular weight-temperature, Figure 8. Similarly, projecting the data in 3D to the x-z or y-z planes resulted in the normal MWD and the concentration-elution temperature profiles, Figure 9.

EXAMPLES 2-6 The polymer samples were separated and analyzed using an aTREF-rGPC device of the type described herein. The basic polymeric properties and activation conditions for the separated and analyzed polymer samples are presented in Table 1. Table 1 EXAMPLE 2 Sample A was separated and analyzed using an aTREF-rGPC apparatus of the type described herein. Sample A was a conventional linear low density polyethylene (LLDPE) resin with a density of 0.921 g / cc and was produced using a Ziegler-Natta catalyst. A three-dimensional presentation of the aTREF-rGPC 2-D data set for Sample A is plotted in Figure 10 under the activation conditions listed in Table I. Note that in Figure 10, the x-axis is the elution temperature, the y-axis is the molecular weight in the logarithmic scale, and the z-axis is the normalized intensity that is a product of the fraction by weight of a fraction of aTREF and the differential intensity of a fraction of MWD (ie, dw / d (Log M)) at a given molecular weight. Figure 10 is a "snapshot" of the 3-D graph at a rotating angle. The results show that there are three regions (or zones) in Figure 10: a low temperature peak corresponding to the soluble fraction of room temperature (RT); a broad peak in the region of moderate temperature raised to about 75 ° C which is believed to originate from the linear low density (LLD) component; and a double peak in the high temperature region ranging from about 85 ° C to 105 ° C. This third peak corresponds to high density polyethylene and homopolymer-like components, respectively, for peaks at about 92 ° C and at about 96 ° C. In Figure 11 the total molecular weight distribution (MWD) profile of the total polymer of Sample A is plotted. This global MWD profile is a projection of the 3-D graph in Figure 10 to its yz plane and is the sum of the MWD profiles of all aTREF fractions presented in Figure 10. The total aTREF profile of Sample A is plotted in Figure 12; is a projection of all aTREF profiles on the 3-D graph in Figure 10 to its x-z plane. This total aTREF profile is a sum of aTREF profiles in all MWD fractions. Note that this fraction of total aTREF can also be obtained independently through the detection unit 55 (see Figure 4) in a continuous manner. The lower right window in Figure 13 is a 2-D contour plot for Sample A. This 2-D contour plot is a projection of the 3-D chart in Figure 10 to its xy plane, in which the color-coded contour level represents the normalized intensity as shown in the z-axis in Figure 10. The upper window and the left window in Figure 13 are the aTREF window and the MWD window, respectively. The axis and left of the aTREF window trace the normalized intensity as a function of elution temperature while the right and right axis plot the accumulated weight fraction as a function of the elution temperature. The aTREF window can plot the total aTREF profile of the total polymer as shown in Figure 12 or an aTREF profile for the polymer with the same given molecular weight. Similarly, the MWD window can plot the global MWD profile of the total polymer as shown in Figure 11 or the MWD profile of a fraction of aTREF at a given elution temperature. The three zones (regions) shown in Figure 10, ie, the low temperature RT soluble zone, the moderate temperature zone LLD, and the HDPE / double peak high temperature homopolymer zone, can also be observed in Figure 13. In Figure 14 the MWD profiles of aTREF fractions of Sample A are plotted at the given elution temperatures. Figure 14 shows that the soluble fraction of RT contains a large amount of high molecular weight components, not simply a component of low MW. In general, all MWD fractions are large regardless of the elution temperature. At higher elution temperatures, such as the 95.8 ° C fraction, it contains more high molecular weight components, but its MW distribution is narrower, ie, with smaller polydispersity index, Mw / Mn. Fractions of aTREF of Sample A in given molecular weights are plotted in Figure 15, in which the x-axis is the elution temperature and the y-axis is the normalized intensity at the given temperature. The data plotted in Figure 15 was extracted from the same data matrix used for Figure 10. Figure 15 shows that a large sample heterogeneity was observed in several MW. For example, at a given molecular weight of 100,000 g / mol (log M = 5.0), there is a broad distribution of chemical composition (CCD) present for the macromolecules of the same MW, due largely to the heterogeneity of branching distribution short chain in the polymer. In this MW, about 13% by weight of the polymer is in the soluble fraction, about 30% by weight of the polymer in the linear low density region (LLD), about 33% by weight of the polymer in the HDPE region, and about 24% by weight of the polymer in the homopolymer-like region. For different molecular weights, its aTREF profiles vary considerably. For example, comparing the fractions of aTREF to Log M = 4.5, and Log M = 6.0, the former has much higher soluble and LLD components while the latter has a much higher homopolymer-like component. The results show that an aTREF-rGPC apparatus is a powerful tool for the characterization of a polymer sample. The type of information plotted in Figure 15 can not be easily obtained by other means unless cross-sectionalization is carried out. Transverse fractionation refers to subjecting the polymer to solvent gradient fractionation (SGF) to separate the polymer according to its molecular weight before fractionation of aTREF is carried out in each and every one of the fractions of SGF that They have been characterized offline, which is a very tedious process.

EXAMPLE 3 Sample B was separated and analyzed using an aTREF-rGPC apparatus of the type described herein. The Sample B is a linear low density polyethylene resin based on chromium catalyst (LDLPE) with a density of 0.923 g / cc. A 2-D contour plot for the activation of Sample B is plotted in Figure 16 under the conditions listed in Table I. There are three regions shown in Figure 16, ie, the peak of soluble fraction, the peak of linear low density (LLD) broad), and the region similar to high density / homopolymer; However, compared to Sample A, Sample B contains less soluble fraction at room temperature (RT) and the soluble fraction has smaller molecular weight. In addition, Sample B contains a higher amount of LLD fraction. Due to differences in activation conditions, the data set used to produce Figure 16 has lower resolution when compared to a similar set of data generated for Sample A, see Figure 13. With reference to Figure 13, the profile of aTREF in the upper window, in which the widest aTREF peaks are observed and the double in Figure 13 has been degraded into a much wider single peak. Note that Sample B is activated under a higher polymer concentration, volume per injection of rGPC larger and, a slower cooling rate, but a higher heating rate during aTREF elution when compared to Sample A.

EXAMPLE 4 Sample C was separated and analyzed using an aTREF-rGPC apparatus of the type described herein. Sample C is a metallocene catalyzed linear low density polyethylene resin (mLLDPE) made with the exclusive technology of Chevron Phillips Chemical Company and having a density of 0.918 g / cc. A 2-D contour plot for activation of Sample C is plotted in Figure 17 under the conditions listed in Table 1. The graph shows an extremely low soluble fraction having a very low molecular weight and a molecular weight distribution very narrow. The results in Figure 17 when compared to conventional LLDPE (Sample A) and Cr-LDLPE (Sample B) show a very homogeneous chemical composition regardless of the molecular weight of the component. However, Sample C contains small amounts of a low molecular weight component which probably has the same chemical composition as the high molecular component, although the low MW component is eluted at lower temperatures due to the final effect of the chain. Figure 17 also clearly shows that there are no components similar to HDPE or homopolymer which is a result that is in agreement with the literature suggesting the homogeneous nature of the metallocene resins.

EXAMPLE 5 Sample D was separated and analyzed using an aTREF-rGPC apparatus of the type described herein. Sample D is a 50:50 mixture of two metallocene resins having a very similar molecular weight and a molecular weight distribution, but with different densities. Figure 18 is a 2-D contour plot for the activation of Sample D under the conditions listed in Table I. The results show that one of the components in Sample D is Sample C, and mLLDPE, and the another is also a metallocene resin, but essentially it is a homopolymer. In addition, although the molecular weight distribution of the polymer mixture looks like a normal metallocene resin with narrow MWD, it has considerable heterogeneity of chemical composition.

Also Sample D contains low soluble fraction as in Sample C and the soluble fraction also has very low MW and narrow MWD (data not shown). Figure 18, the 2-D profile shows three peaks; a peak at approximately 80 ° C in the LLD region, and another peak at approximately 94 ° C in the high density polyethylene (HDPE) region, and yet another peak at 98 ° C in the homopolymer-like region. In Sample D, the LLD peak is changed to lower temperature when compared to Figure 17. This peak also has reduced total intensity (approximately 30%) when compared to the initial content (50%). Clearly, a little of the component of Sample C in this mixture elutes at higher temperatures. This result suggests some interaction, probably co-crystallization, which may have occurred between these two components in Sample D. The results demonstrate that the inventive method and the device described herein can be used for the study of polymer blends.

EXAMPLE 6 Sample E was separated and analyzed using an aTREF-rGPC apparatus of the type described herein. Sample E is bimodal HDPE with a density of 0.961 g / cc consisting of two components: one is a high MW copolymer and the other is a low MW homopolymer, both of which are made with a conventional Ziegler-Natta catalyst. . A 2-D contour plot for the activation of Sample E is plotted in Figure 19 under conditions listed in Table I. Figure 19 shows that as expected for HDPE, Sample E contains a low amount of the fraction soluble to RT, which has both a low MW and a narrow MWD. Most of the components (approximately 80%) in Sample E are eluted outward in the HDPE-like and homopolymer region (90 ° C-105 ° C). In this region, when the elution temperature is increased, the narrow dominant MW low peak is replaced by the high MW component. The high MW component of the copolymer component co-elutes with the MW component raised from the low MW homopolymer. Furthermore, for Sample E there is approximately 20% of the polymer eluting at a temperature below 90 ° C, as can be demonstrated from the TREF profile in the upper window. These low temperature fractions extend through a large temperature range, resulting in a low concentration for each fraction. As a result, its polymer compositions are not clearly shown at the contour level given in Figure 19. Therefore, in order to observe the chemical composition of low concentration components, it is necessary to decrease the contour level. A part of Figure 19 is traced in Figure 20, but with a reduced boundary level and a limited temperature range (40 ° C - 90 ° C). At the decreased contour level, it is clear that the components that elute at low temperatures are bimodal. The high molecular weight species in these bimodal, presumably the high MW copolymer component, co-elute at given temperatures with species in the low MW homopolymer component. This results in Figure 19 strongly suggesting that there is a high compositional heterogeneity present in the high MW copolymer component in Sample E. Polymers with a remarkably different composition can co-elute together as long as they have the same crystallization capacity. The results demonstrate that the inventive methods and devices described herein can also be used for the study of high performance resin with a designed chemical composition. Although the preferred embodiments of the invention have been shown and described, modifications thereof may be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described herein are exemplary only, and are not intended to be limiting. Many variations and modifications of the invention described herein are possible and are within the scope of the invention. In the case where numerical ranges or limitations are expressly set forth, such explicit ranges or limitations should be understood to include iterative ranges or limitations of how much they fall within the expressly established ranges or limitations (e.g., from about 1 to about 10, even, 2, 3, 4, etc., more than 0.10 even 0.11, 0.12, 0.13, etc.) The use of the term "optionally" with respect to any element of a claim is intended to mean that the object element is required, or alternatively, it is not required. Both alternatives are intended to be within the scope of the claim. The use of broader terms such as, include, include, have, etc., should be understood to provide support for narrower terms such as consisting of, consisting essentially of, substantially comprised of, etc. Accordingly, the scope of protection is not limited by the description set forth above, but is limited only by the claims that follow, that scope includes all equivalents of the subject matter of the claims. Each and every claim is incorporated in the specification as an embodiment of the present invention. Thus, the claims are a further description and are in addition to the preferred embodiments of the present invention. The descriptions of all patents, patent applications and publications cited herein are therefore incorporated by reference, to the extent that they provide exemplary, procedural or other additional details by those set forth herein.

Claims (22)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the property described in the following claims is claimed as property.
2. CLAIMS 1. An analytical method, characterized in that it comprises: (a) performing a first fractionation of a polymer sample based on differences in crystallization capacity to provide a first set of sample fractions; (b) perform a first analysis in the first set of sample fractions; (c) performing a second fractionation of the first set of sample fractions to produce a second set of the sample fractions; (d) performing a second analysis in the second set of sample fractions; and (e) synchronizing the first fractionation and the second fractionation to provide approximately concurrent analysis of the polymer sample. The method according to claim 1, characterized in that the polymer sample comprises a semicrystalline polymer, a polymer mixture, a polymer whose solubility changes as a function of the temperature of the solvent or combinations thereof.
3. 3. The method according to claim 1, characterized in that the first fractionation is an elution fractionation of temperature rise.
4. 4. The method according to claim 1, characterized in that the first analysis comprises determining the chemical composition.
5. 5. The method according to claim 1, characterized in that the second fractionation is based on the hydrodynamic volume.
6. 6. The method according to claim 1, characterized in that the second fractionation is a fast gel permeation chromatography.
7. 7. The method of compliance with the claim

   6, further characterized in that it comprises heating the first set of sample fractions before rapid gel permeation chromatography.
8. 8. The method according to claim 1, characterized in that the second analysis comprises determining the molecular weight, the average molecular weight, the molecular weight distribution or combinations thereof.
9. 9. The method according to claim 1, characterized in that it is implemented through a computer controlled device.
10. The method according to claim 1, further characterized in that it comprises graphically representing the polymer composition, the molecular weight and the molecular weight distribution of the polymer sample.
11. 11. A device for characterizing a polymer sample comprises: a first column for fractionating the polymer sample based on differences in crystallization capacity to obtain a first set of the sample fractions; a first detection device in fluid communication with the first column and receiving at least a portion of the first set of the sample fractions; a second column in fluid communication with the first column, the first detection device or both to receive at least a portion of the first set of the sample fractions, wherein the portion of the first set of the sample fractions is fractioned to produce a second set of sample fractions; and a second detection device in fluid communication with the second column and receiving at least a portion of the second set of sample fractions, wherein the first and second columns are synchronized to provide approximately concurrent analysis of the polymer sample.
12. The device according to claim 11, characterized in that the first column is an elution fractionation column of analytical temperature elevation.
13. 13. The device according to claim 11, characterized in that the second column is a rapid gel permeation chromatography column.
14. 14. The device according to claim 11, characterized in that the first column is coupled to a first pump for transporting fluid thereto and the second column is coupled to a second pump for transporting fluid thereto.
15. 15. The device according to claim 11, characterized in that the first detection device comprises a spectrometer, a photometer, a viscometer, or combinations thereof.
16. The device according to claim 11, characterized in that the second column comprises a hydrophobic interaction column, an ion exchange column, a high performance liquid chromatography column (HPLC) or combinations thereof.
17. The device according to claim 11, characterized in that the second detection device is an optical device.
18. The device according to claim 11, characterized in that the first detection device comprises an infrared detector with Fourier transform, a multiple angle light scattering detector, a viscometer, or combinations thereof and the second device of detection comprises an infrared measuring device, a differential refractometer or combinations thereof.
19. The device according to claim 11, further characterized in that it comprises at least one multiport valve that transports samples from a sample reservoir to the first column, transporting at least a portion of the first set of sample fractions to the second column. , or combinations thereof.
20. The device according to claim 19, characterized in that the multiport valve comprises at least six ports.
21. The device according to claim 11, further characterized in that it comprises a computer coupled to the first and second columns and to the first and second detection devices and synchronizes the device to provide concurrent analysis of the polymer sample.
22. 22. An analytical method, characterized in that it comprises: introducing a sample to an analytical device that has an elution fractionation of synchronized analytical temperature elevation and elements of rapid gel permeation chromatography; operate the analytical device; and determining the composition, molecular weight and molecular weight distribution of a polymer sample in less than about 24 hours.